TWI516475B - Compound having indenocarbazole ring structure, and organic electroluminescent device - Google Patents

Description

Compound and organic electroluminescent device having an indolocarbazole ring structure

The present invention relates to a compound suitable for use in an organic electroluminescent device of a self-luminous element of various display devices, and in particular to a compound having an indolocarbazole ring structure and a compound having the same Electroluminescent element.

Since the organic electroluminescence device is a self-luminous element, it is brighter than the liquid crystal element and is excellent in visibility, and can be clearly displayed.

In 1987, CWTang et al. of Eastman Kodak Co., Ltd. applied an organic electroluminescent device using an organic material by developing a laminated structural element that shares various functions in each material. They are laminated with an electron-transporting phosphoric acid (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq ₃ ) and an aromatic amine compound capable of transporting holes, and injecting the charges of both into the phosphor layer. In addition, high lightness of 1000 cd/m ² or more is obtained with a voltage of 10 V or less (see, for example, Patent Document 1 and Patent Document 2).

In order to practically improve the organic electroluminescence device, various functions have been further subdivided, and the anode, the hole injection layer, the hole transport layer, the light-emitting layer, and the electron transport layer are sequentially disposed on the substrate. An electroluminescent element made of an electron injecting layer or a cathode achieves high efficiency and durability (for example, see Non-Patent Document 1).

Further, in order to further improve the luminous efficiency, attempts have been made to utilize triplet excitons, and the use of phosphorescent emitters has been studied (for example, refer to Non-Patent Document 2).

The light-emitting layer can also be produced by doping a phosphor or a phosphorescent light-emitting substance in a charge transporting compound generally called a host material. As described in the prep draft of the above-mentioned workshop, the selection of the organic material in the organic electroluminescence element greatly affects various characteristics such as efficiency or durability of the element.

In the organic electroluminescent device, charges injected from the two electrodes are recombined in the light-emitting layer to obtain light emission. However, it is important to transfer the holes and electron charges to the light-emitting layer with high efficiency, thereby improving hole injection. The electron blocking property of electrons blocking the cathode injection is increased to increase the probability of recombination of holes and electrons, and further, by excitons generated in the light-emitting layer, high luminous efficiency can be obtained. Therefore, the function achieved by the hole transporting material is important, and therefore, a hole transporting material having high hole injectability, large mobility of the hole, high electron blocking property, and high durability against electrons is sought.

In addition, regarding the life of the component, the heat resistance or amorphousness of the material is also important. In the case of a material having low heat resistance, the heat generated during the driving of the element causes thermal decomposition even at a low temperature, and the material deteriorates. If the material is low in amorphousity, the film will be crystallized even in a short period of time, and the element will deteriorate. Therefore, the material to be used has high heat resistance and good amorphous properties.

N,N'-diphenyl-N,N'-bis(α-naphthyl)benzidine (hereinafter abbreviated as NPD) or N-N'-diphenyl-N,N'-di(α-naphthyl)benzidine (hereinafter abbreviated as NPD) is known as a hole transporting material used in an organic electroluminescence device. Various aromatic amine derivatives (for example, refer to Patent Document 1 and Patent Document 2). Although NPD has a good hole transporting ability, the glass transition point (Tg) which is an index of heat resistance is a low value of 96 ° C, and thus the element characteristics are lowered due to crystallization under high temperature conditions (for example, refer to the non-patent Document 3). Further, among the aromatic amine derivatives described in Patent Document 1 and Patent Document 2, a compound having an excellent mobility of a mobility of 10 ^-3 cm ² /Vs or more is known. Since the electron blocking property is insufficient, a part of the electrons pass through the light-emitting layer, and the improvement of the light-emitting efficiency cannot be expected. In order to increase the efficiency, the electronic barrier property is high and the film is more stable. A material with high heat resistance.

An aromatic amine compound having a substituted carbazole structure (for example, Compound A and Compound B) represented by the following formula is proposed as a compound having improved properties such as heat resistance and hole injectability (for example, refer to Patent Documents 3 and 4). .

[Chemical 1]

[Chemical 2]

However, although heat resistance, luminous efficiency, and the like are improved in an element using such a compound in a hole injection layer or a hole transport layer, it cannot be said to be sufficient; further, low driving voltage or current efficiency is insufficient. . Therefore, it has been demanding lower driving voltages or higher luminous efficiency.

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 8-048656

Patent Document 2: Japanese Patent No. 3194657

Patent Document 3: Japanese Laid-Open Patent Publication No. 2006-151979

Patent Document 4: WO2008/62636

[Non-patent literature]

Non-Patent Document 1: The 9th Workshop of the Applied Physics Society, 55-61 (2001)

Non-Patent Document 2: The 9th Workshop of the Applied Physics Society, 23-31 (2001)

Non-Patent Document 3: Organic EL Symposium Third Regular Meeting Pre-collection 13~14 (2006)

Non-Patent Document 4: J. Org. Chem., 60, 7508 (1995)

Non-Patent Document 5: Synth. Commun., 11, 513 (1981)

An object of the present invention is to provide an organic compound which is used as a material for high efficiency and high durability of an organic electroluminescence device, which has excellent hole injection and transmission properties, electronic barrier capability, and stability in a thin film state. Excellent characteristics such as high efficiency and high luminous efficiency; the present invention further uses this compound to provide an organic electroluminescent device having high efficiency and high durability.

The physical properties required for the organic compound to be provided by the present invention include (1) excellent injection characteristics of the hole, (2) large mobility of the hole, and (3) excellent electron blocking ability, and (4) film. The state is stable and (5) excellent in heat resistance. Further, as the physical properties required for the organic electroluminescence device to be provided by the present invention, (1) high luminous efficiency and power supply efficiency, (2) low initial light emission voltage, and (3) low practical driving voltage .

In order to achieve the above object, the inventors of the present invention have been able to expect a high degree of hole mobility from the planarity of the indolocarbazole ring structure, a high triplet energy level can be expected, and excellent electron blocking properties can be expected. Further, it is expected that excellent heat resistance and film stability, and an aromatic tertiary amine structure having high hole injection and transport ability, thereby designing and chemically synthesizing a compound having an indolocarbazole ring structure and an aromatic tertiary amine structure The use of the compound as a result of various evaluations of the characteristics of the element was carried out by experimenting with various organic electroluminescent elements, thereby completing the present invention.

That is, the present invention is a compound having an indolocarbazole ring structure represented by the following formula (1).

[Chemical 3]

(wherein A represents a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring or a substituted or unsubstituted condensed polycyclic aromatic divalent group, and Ar ₁ , Ar ₂ and Ar ₃ may be mutually The same or different, which represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. Here, A and Ar ₂ or Ar ₂ It is also possible to form a ring with Ar ₃ through a single bond or a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom. R ₁ to R ₉ may be the same or different from each other, and are a hydrogen atom or a heavy hydrogen atom. a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, may have a substituent a cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted a substituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also pass through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or sulfur. The atoms are bonded to each other to form a ring. R ₁₀ and R ₁₁ may be the same or different from each other, and may be a linear or branched alkyl group having 1 to 6 carbon atoms and a carbon atom which may have a substituent. a cycloalkyl group of 5 to 10, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched carbon number of 1 to 6 which may have a substituent Alkoxy group, cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic A group-based or substituted or unsubstituted aryloxy group may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

Further, the present invention is a compound having an indolocarbazole ring structure represented by the following formula (2).

[Chemical 4]

(wherein, Ar ₁ and Ar ₄ may be the same or different from each other, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. R ₁ to R ₉ and R ₁₂ to R ₂₀ may be the same or different from each other, and are a hydrogen atom, a heavy hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, and a carbon atom which may have a substituent of 1 to a linear or branched alkyl group of 6 or a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 10 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, and a substitution Or an unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also pass through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom bonded to each other to form a ring _{.R 10, R 11, R 21} , R 22 may be the same or different It may be a linear or branched alkyl group having 1 to 6 carbon atoms of a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and 2 to 10 carbon atoms which may have a substituent a linear or branched alkenyl group of 6 or a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, and a cycloalkane having 5 to 10 carbon atoms which may have a substituent a substituted, unsubstituted or substituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted aryloxy group, R ₁₀ and R ₁₁ or R ₂₁ and R ₂₂ may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.)

Further, the present invention is a compound having an indolocarbazole ring structure represented by the following formula (3).

[Chemical 5]

(wherein A represents a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group, and Ar ₁ , Ar ₂ , and Ar _{3 are} mutually The same or different, which may represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. Here, A and Ar ₂ or Ar ₂ and Ar ₃ may also be bonded to each other through a single bond or a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom. R ₁ to R ₉ may be the same or different, and are hydrogen atoms and heavy hydrogen. An atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and a cycloalkane having 5 to 10 carbon atoms which may have a substituent a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, may have a substitution a cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or a non-substituted a substituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also pass through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or sulfur The atoms are bonded to each other to form a ring. R ₁₀ and R ₁₁ may be the same or different from each other, and may be a linear or branched alkyl group having 1 to 6 carbon atoms and a carbon atom which may have a substituent. a cycloalkyl group of 5 to 10, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched carbon number of 1 to 6 which may have a substituent Alkoxy group, cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic A group-based or substituted or unsubstituted aryloxy group may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

Further, the present invention is a compound having an indolocarbazole ring structure represented by the following formula (4).

[Chemical 6]

(wherein, Ar ₁ and Ar ₄ may be the same or different from each other, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. R ₁ to R ₉ and R ₁₂ to R ₂₀ may be the same or different from each other, and are a hydrogen atom, a heavy hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, and a carbon atom which may have a substituent of 1 to a linear or branched alkyl group of 6 or a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 10 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, and a substitution Or an unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also pass through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom bonded to each other to form a ring _{.R 10, R 11, R 21} , R 22 may be the same or different It may be a linear or branched alkyl group having 1 to 6 carbon atoms of a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and 2 to 10 carbon atoms which may have a substituent a linear or branched alkenyl group of 6 or a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, and a cycloalkane having 5 to 10 carbon atoms which may have a substituent a substituted, unsubstituted or substituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted aryloxy group, R ₁₀ and R ₁₁ or R ₂₁ and R ₂₂ may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.)

Further, the present invention is an organic electroluminescence device having a pair of electrodes and an organic layer sandwiching at least one layer therebetween, the organic electroluminescence device being characterized by using the above formula (1) to (4) Any one of the compounds having an indolocarbazole ring structure as a constituent material of at least one organic layer.

In the general formulae (1) to (4), the "linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent" represented by R ₁ to R ₂₂ may have a substituent. "Cycloalkyl group having 5 to 10 carbon atoms" or "linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent""linear chain having 1 to 6 carbon atoms or a branched alkyl group, a "cycloalkyl group having 5 to 10 carbon atoms", or a "linear or branched alkenyl group having 2 to 6 carbon atoms", specifically, a methyl group, Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopentyl, cyclohexyl, 1-adamantyl , 2-adamantyl, vinyl, propenyl, isopropenyl, 2-butenyl, and the like. Further, the groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

The "linear or branched alkyl group having 1 to 6 carbon atoms having a substituent" represented by R ₁ to R ₂₂ in the general formulae (1) to (4), and "carbon atom having a substituent" The "substituent" in the number of the cycloalkyl group of 5 to 10 or the "linear or branched alkenyl group having 2 to 6 carbon atoms having a substituent", specifically, a heavy hydrogen atom , a cyano group, a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; An alkenyl group such as a propenyl group; an aryloxy group such as a phenoxy group or a tolyloxy group; an arylalkoxy group such as a benzyloxy group or a phenethyloxy group; a phenyl group, a biphenyl group, a triphenylene group, a naphthyl group; An aromatic hydrocarbon group or a condensed polycyclic aromatic group such as an onion group, a phenanthryl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluoranthene group, or a triphenylenyl group; a pyridyl group, a decyl group, a pyran group; Base, thienyl, furyl, pyrrolyl, quinolyl, isoquinolinyl, benzoanyl, benzothienyl, fluorenyl, oxazolyl, benzoxazolyl, benzothiazolyl, quin Minoline group Xalyl), benzimidazolyl, pyrazolyl, dibenzoanyl, dibenzothiophenyl, porphyrin or the like, such as an aromatic heterocyclic group, which may be further substituted with other substituents Replace. Further, the substituent groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

The linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent represented by R ₁ to R ₂₂ in the general formulae (1) to (4) or "may have a substituent" In the cycloalkyloxy group having 5 to 10 carbon atoms, "a linear or branched alkoxy group having 1 to 6 carbon atoms" or "a cycloalkoxy group having 5 to 10 carbon atoms", specifically Examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a tertiary butoxy group, a n-pentyloxy group, a n-hexyloxy group, a cyclopentyloxy group, and a ring. Hexyloxy, cycloheptyloxy, cyclooctyloxy, 1-adamantyloxy, 2-adamantyloxy and the like. Further, the groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

As the "linear or branched alkoxy group having 1 to 6 carbon atoms having a substituent" represented by R ₁ to R ₂₂ in the general formulae (1) to (4) or "carbon having a substituent" Specific examples of the "substituent" in the cycloalkyloxy group having 5 to 10 atomic atoms include a heavy hydrogen atom, a cyano group, a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; an alkenyl group such as a propenyl group; an aryloxy group such as a phenoxy group or a tolyloxy group; An arylalkoxy group such as a phenylethoxy group; a phenyl group, a biphenyl group, a triphenylene group, a naphthyl group, an onion group, a phenanthryl group, an anthracenyl group, an anthracenyl group, an anthracenyl group, a fluorenyl group, a fluorenyl group, An aromatic hydrocarbon group or a condensed polycyclic aromatic group such as a phenyl group; a pyridyl group, a decyl group, a pyranyl group, a thienyl group, a furyl group, a pyrrolyl group, a thienyl group, a quinolyl group, an isoquinolyl group, a benzo group Meryl, benzothienyl, fluorenyl, oxazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzopyranyl, dibenzo Thienyl, porphyrin Aromatic heterocyclic group such as a group, these substituent groups may further be substituted with additional substituents. Further, the substituent groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

Examples of the "substituted or unsubstituted aromatic hydrocarbon group" represented by R ₁ to R ₂₂ and Ar ₁ to Ar ₄ in the general formulae (1) to (4), and "substituted or unsubstituted aromatic heterocyclic group", The "aromatic hydrocarbon group", the "aromatic heterocyclic group" or the "condensed polycyclic aromatic group" in the "substituted or unsubstituted condensed polycyclic aromatic group", specifically, a phenyl group, Biphenyl, tert-triphenyl, naphthyl, onion, phenanthryl, anthracenyl, fluorenyl, fluorenyl, fluorenyl, fluoranthenyl, triphenylene, pyridyl, yl, pyranyl, Thienyl, quinolyl, isoquinolyl, benzopyranyl, benzothienyl, fluorenyl, oxazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl , pyrazolyl, dibenzoanyl, dibenzothiophenyl, and porphyrin. Further, the groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

Here, as the "aromatic heterocyclic group" in the "substituted or unsubstituted aromatic heterocyclic group" represented by Ar ₂ to Ar ₄ in the general formulae (1) to (4), thiophene is preferred. A sulfur-containing aromatic heterocyclic group such as a benzothiophenyl group, a benzothiazolyl group or a dibenzothienyl group.

In addition, as a bonding position of a "substituted or unsubstituted aromatic heterocyclic group" represented by R ₁ to R ₂₂ and Ar ₁ in the general formulae (1) to (4), from the viewpoint of stability and heat resistance In view of the above, it is preferred to bond to a carbon atom of an "aromatic heterocyclic group".

Examples of the "substituted aromatic hydrocarbon group" represented by R ₁ to R ₂₂ and Ar ₁ to Ar ₄ in the general formulae (1) to (4), "substituted aromatic heterocyclic group", or "substituted condensed polycyclic aromatic group" Specific examples of the "substituent" in the group include a heavy hydrogen atom, a trifluoromethyl group, a cyano group, a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, etc., having a carbon number of 1 to 6 a chain or branched alkyl group; a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; an alkenyl group such as a propenyl group; a benzyl group or a naphthyl group; An aralkyl group such as a methyl group or a phenethyl group; an aryloxy group such as a phenoxy group or a tolyloxy group; an arylalkoxy group such as a benzyloxy group or a phenethyloxy group; a phenyl group, a biphenyl group, and a triphenyl group; An aromatic hydrocarbon group or a condensed polycyclic aromatic group such as a naphthyl group, an onion group, a phenanthryl group, an anthracenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluoranthene group or a triphenylene group; a pyridyl group, a decyl group, a pyran group; Base, thienyl, furanyl, Pyrrolyl, thienyl, quinolyl, isoquinolyl, benzopyranyl, benzothienyl, fluorenyl, oxazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzene An aromatic heterocyclic group such as an imidazolyl group, a pyrazolyl group, a dibenzoanyl group, a dibenzothiophenyl group or a porphyrin group; an arylvinyl group such as a styryl group or a naphthylvinyl group; an acetyl group or a benzamidine group; a thiol group; a dialkylamino group such as a dimethylamino group or a diethylamino group; a disubstituted amino group substituted with an aromatic hydrocarbon group or a condensed polycyclic aromatic group such as a diphenylamino group or a dinaphthylamino group; a diarylalkylamino group such as a dibenzylamino group or a diphenylethylamino group; a disubstituted amino group substituted with an aromatic heterocyclic group such as a dipyridylamino group or a dithienylamino group; and a dipropenylamine; a disubstituted amino group substituted with an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, an aromatic heterocyclic group, or an alkenyl group, and the like Substituents can also be further substituted. Further, the substituents may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

Specific examples of the "aryloxy group" in the "substituted or unsubstituted aryloxy group" represented by R ₁ to R ₂₂ in the general formulae (1) to (4) include phenoxy group and phenoxy group. Phenoxy, tert-triphenyloxy, naphthyloxy, onionoxy, phenanthryloxy, nonyloxy, decyloxy, decyloxy, decyloxy and the like. Further, the groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

Specific examples of the "substituent" in the "substituted aryloxy group" represented by R ₁ to R ₂₂ in the general formulae (1) to (4) include the following groups: a heavy hydrogen atom and a trifluoro group. Methyl, cyano, nitro; halogen atom such as fluorine atom, chlorine atom, bromine atom or iodine atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl a linear or branched alkyl group having 1 to 6 carbon atoms such as n-pentyl, isopentyl, neopentyl or n-hexyl; and 1 to 6 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group; a linear or branched alkoxy group of 6; an alkenyl group such as a propenyl group; an aralkyl group such as a benzyl group, a naphthylmethyl group or a phenethyl group; an aryloxy group such as a phenoxy group or a tolyloxy group; An arylalkoxy group such as phenethyloxy; phenyl, biphenyl, terphenyl, naphthyl, onion, phenanthryl, anthracenyl, fluorenyl, fluorenyl, fluorenyl, fluorenyl, fluorenyl An aromatic hydrocarbon group such as a triphenylene group or a condensed polycyclic aromatic group; a pyridyl group, a decyl group, a pyranyl group, a thienyl group, a furyl group, a pyrrolyl group, a thienyl group, a quinolyl group, an isoquinolyl group, a benzoan group Base, benzothienyl, fluorenyl, An aromatic heterocyclic group such as an azole group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzoanyl group, a dibenzothiophenyl group or a porphyrin group; An arylvinyl group such as a styryl group or a naphthylvinyl group; a fluorenyl group such as an ethyl group or a benzhydryl group; a dialkylamino group such as a dimethylamino group or a diethylamino group; a diphenylamino group and a dinaphthyl group; a disubstituted amino group substituted with an aromatic hydrocarbon group or a condensed polycyclic aromatic group such as an amine group; a diarylalkylamino group such as a dibenzylamino group or a diphenylethylamino group; a dipyridylamino group and a dithienyl group; a disubstituted amino group such as an amine group substituted with an aromatic heterocyclic group; a dienylamino group such as a diacryloylamino group; or an alkyl group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group, an aralkyl group, or an aromatic group A disubstituted amino group substituted with a heterocyclic group or a substituent selected by an alkenyl group, which may be further substituted. Further, the substituents may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

The divalent group of the substituted or unsubstituted aromatic hydrocarbon represented by A in the general formulae (1) and (3), the "divalent group of the substituted or unsubstituted aromatic heterocyclic ring", or the "substituted" Or a divalent group of an aromatic hydrocarbon in an unsubstituted condensed polycyclic aromatic divalent group, or a divalent group of an aromatic heterocyclic ring, or a divalent group of a condensed polycyclic aromatic group, Specifically, examples thereof include a phenylene group, a biphenylene group, a terphenylene group, a tetrakisphenylene group, an anthranyl group, a fluorene group, a phenanthrene group, and a stretching group. Sulfhydryl, phenanthrenyl, anthracene, anthracene, anthracene, fluoranthene, triphenylenylene, stilbene, pyrimidinyl, quinolinyl, isoprene Quinolinyl, hydrazino, carbazolyl, quinoxalylene, benzimidazolyl, pyrazolyl, naphthyl, phenanthroline, extenoid, exo Thienyl, benzothiophenyl, benzothiazolyl, dibenzothiophenyl, and the like.

Here, the "divalent group of the aromatic heterocyclic ring" in the "divalent group of the substituted or unsubstituted aromatic heterocyclic ring" represented by A in the general formulae (1) and (3) is preferably a divalent group of a sulfur-containing aromatic heterocyclic ring such as a thienyl group, a benzothienyl group, a benzothiazolyl group or a dibenzothiophene group.

Further, these groups may also be a "substituted or unsubstituted aromatic hydrocarbon group" represented by Ar ₂ in the general formulae (1) and (3), a "substituted or unsubstituted aromatic heterocyclic group", or The "substituted or unsubstituted condensed polycyclic aromatic group" is bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

The divalent group of the substituted aromatic hydrocarbon represented by A in the general formulae (1) and (3), the "divalent group of the substituted aromatic heterocyclic ring", or the "divalent group of the substituted condensed polycyclic aromatic group" Specific examples of the "substituent" in the group include a hydrogen atom, a cyano group, a nitro group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; , n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, etc., linear or branched with 1 to 6 carbon atoms Alkyl group; a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; an alkenyl group such as a propenyl group; a benzyl group, a naphthylmethyl group or a phenyl group An arylalkyl group; an aryloxy group such as a phenoxy group or a tolyloxy group; an arylalkoxy group such as a benzyloxy group or a phenethyloxy group; a phenyl group, a biphenyl group, a triphenylene group, a naphthyl group, an onion group An aromatic hydrocarbon group or a condensed polycyclic aromatic group such as a phenanthryl group, a thiol group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluoranthene group or a hydrazine group; a pyridyl group, a decyl group, a pyranyl group, a thienyl group, Furanyl, pyrrole , thienyl, quinolyl, isoquinolyl, benzopyranyl, benzothienyl, fluorenyl, oxazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazole An aromatic heterocyclic group such as a pyrazole group, a dibenzoanyl group, a dibenzothiophenyl group or a porphyrin group; an arylvinyl group such as a styryl group or a naphthylvinyl group; an ethyl fluorenyl group or a benzhydryl group; Further, the substituents may be further substituted. Further, the substituents may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

Further, a compound having an indolocarbazole ring structure represented by the above formula (3) is used in an organic electroluminescence device, and preferably has the following formula (3-1) and formula (3- 2) A compound having the structure of an indolocarbazole ring represented by the formula (3-3) or the formula (3-4).

[Chemistry 7]

(wherein, Ar ₁ , Ar ₂ and Ar ₃ may be the same or different from each other, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic ring. The aromatic group. R ₁ to R ₉ may be the same or different from each other, and are a hydrogen atom, a heavy hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, and a carbon atom having a substituent of 1 to 6 a chain or branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, may have a substitution a linear or branched alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 5 to 10 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted group Aromatic heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic group, or substituted or unsubstituted aryloxy group, which may also pass through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom. Bonding each other to form a ring.)

[化8]

(wherein Ar ₂ and Ar ₃ may be the same or different from each other, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. R ₁ to R ₉ may be the same or different from each other, and are a hydrogen atom, a heavy hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear group having 1 to 6 carbon atoms which may have a substituent or a branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a carbon which may have a substituent a linear or branched alkoxy group having 1 to 6 atoms, a cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group a heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom. Form a ring.)

[Chemistry 9]

(wherein, Ar ₁ and Ar ₃ may be the same or different from each other, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. R ₁ to R ₉ may be the same or different from each other, and are a hydrogen atom, a heavy hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear group having 1 to 6 carbon atoms which may have a substituent or a branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a carbon which may have a substituent a linear or branched alkoxy group having 1 to 6 atoms, a cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group a heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom. Form a ring.)

[化10]

(wherein Ar ₁ represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. R ₁ to R ₉ may be the same as each other. Differently, it is a hydrogen atom, a heavy hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and may have a substituent. a cycloalkyl group having 5 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched carbon number of 1 to 6 which may have a substituent Alkoxy group, cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensation A cycloaromatic group or a substituted or unsubstituted aryloxy group may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

The compound having the structure of the indolocarbazole ring represented by the formula (1) of the present invention is a novel compound having excellent electron blocking ability, excellent amorphous property, and film state than the conventional hole transporting material. stable.

The compound having an indolocarbazole ring structure represented by the formula (1) of the present invention can be used for a hole injection layer and/or hole transport as an organic electroluminescence device (hereinafter, simply referred to as an organic EL device). The constituent material of the layer. By using a material having a higher hole injectability, a higher mobility, a higher electron blocking property, and a higher stability to electrons than a conventional material, excitons generated in the light-emitting layer can be enclosed, and further The probability of recombination of the hole and the electron is increased, and the high luminous efficiency is obtained, and the driving voltage is lowered and the durability of the organic EL element is improved.

The compound having an indolocarbazole ring structure represented by the formula (1) of the present invention can be used as a constituent material of an electron blocking layer of an organic EL device. By using a material which is excellent in electron blocking ability and excellent in hole transportability and high in film state compared with a conventional material, it has high luminous efficiency and also has a low driving voltage and an improved current. Resistance, and the effect of increasing the maximum luminance of the organic EL element.

The compound having an indolocarbazole ring structure represented by the formula (1) of the present invention can be used as a constituent material of a light-emitting layer of an organic EL device. By using a material of the present invention which is superior in hole transportability and wide in band gap as a host material of a light-emitting layer, a phosphorescent or phosphorescent material called a dopant is used. When the illuminant is used as a light-emitting layer, it has an effect of realizing an organic EL element which lowers the driving voltage and improves the light-emitting efficiency.

Since the organic EL device of the present invention has a large mobility of a hole, an excellent electron blocking ability, an excellent amorphous property, and a stable film state, an indolocarbazole ring is used as compared with a conventional hole transporting material. The compound is constructed so that high efficiency and high durability can be achieved.

The compound having an indolocarbazole ring structure of the present invention is suitable as a constituent material of a hole injection layer, a hole transport layer, an electron blocking layer, or a light-emitting layer of an organic EL element, which has excellent electron blocking ability and is non- The crystallinity is good, the film state is stable, and the heat resistance is excellent. The organic EL device of the present invention has high luminous efficiency and power supply efficiency, whereby the practical driving voltage of the device can be lowered. The light-emitting starting voltage can be lowered and the durability can be improved.

The compound having an indolocarbazole ring structure of the present invention is a novel compound which can be synthesized, for example, by the following method. For example, N-(9,9-dimethylindol-2-yl)-2-bromoaniline is synthesized by the reaction of 2-bromoaniline with 9,9-dimethyl-2-iodoindole By carrying out a cyclization reaction, 12,12-dimethyl-10,12-dihydro-indolo[2,1-b]carbazole can be synthesized. Then, by performing a condensation reaction of the 12,12-dimethyl-10,12-dihydro-indolo[2,1-b]carbazole with iodobenzene, the synthesis reaction can be carried out 12,12- Dimethyl-10-phenyl-10,12-dihydroindeno[2,1-b]carbazole. Further, by bromination of 12,12-dimethyl-10-phenyl-10,12-dihydroindolo[2,1-b]carbazole by N-bromosuccinimide or the like, It is possible to synthesize 7-bromo-12,12-dimethyl-10-phenyl-10,12-dihydroindolo[2,1-b]carbazole. Here, by using 2-bromoaniline, 2-iodoindole, or an iodine compound substituted with a corresponding substituent as a raw material, 10,12-dihydroindole substituted by a corresponding substituent can be synthesized [2,1 -b] Bromine substitution of carbazole.

Further, it is synthesized by reacting an aryl halide substituted with various diarylamine groups with a pinacolborane or a bis(pinacolato) diboron. The boric acid or boric acid ester (for example, refer to Non-Patent Document 4), and the bromine substitution of 10,12-dihydroindolo[2,1-b]carbazole substituted with the above-mentioned equivalent substituent is subjected to Suzuki coupling ( A compound having an indolocarbazole ring structure of the present invention can be synthesized by a cross-coupling reaction such as Suzuki coupling (for example, refer to Non-Patent Document 5).

Among the compounds having an indolocarbazole ring structure represented by the formula (1), specific examples of preferred compounds are shown below, but the present invention is not limited to the compounds.

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The purification of these compounds is carried out by purification by column chromatography, adsorption purification using tannin extract, activated carbon, activated clay, or the like by recrystallization or crystallization of a solvent. Identification of the compounds was carried out by NMR analysis. As a physical property value, a glass transition point (Tg) and a work function were measured. The glass transition point (Tg) is an indicator of the stability of the film state, and the work function is an indicator of the hole transportability.

The glass transition point (Tg) was measured using a powder using a high-sensitivity differential scanning calorimeter (manufactured by Bruker-AXS, DSC3100S).

The work function was performed by fabricating a 100 nm thin film on an ITO substrate, and measuring it using an atmospheric photoelectron spectroscope (manufactured by Riken Keiki Co., Ltd., AC-3 type).

The structure of the organic EL device of the present invention may be a structure in which an anode, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, and a cathode are sequentially formed on a substrate; or, in an anode and electricity Those having a hole injection layer between the hole transport layers and having an electron injection layer between the electron transport layer and the cathode. In the multilayer structure, several layers of the organic layer may be omitted, and for example, a structure having an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode on the substrate may be formed.

As the anode of the organic EL device of the present invention, an electrode material having a large work function such as ITO or gold is used. As the hole injection layer of the organic EL device of the present invention, in addition to the compound having the structure of the indolocarbazole ring represented by the formula (1) of the present invention, a purple compound represented by copper indigo may be used. A material such as a starburst-type triphenylamine derivative, various triphenylamine tetramers, a hexacyanoazinium-triazine-like acceptor-like heterocyclic compound or a coated polymer material. In addition to the vapor deposition method, film formation of these materials can be carried out by a known method such as a spin coating method or an inkjet method.

As the hole transport layer of the organic EL device of the present invention, N,N'-diphenyl-N may be used in addition to the compound having an indolocarbazole ring structure represented by the formula (1) of the present invention. N'-di(m-tolyl)benzidine (hereinafter abbreviated as TPD), N,N'-diphenyl-N,N'-bis(?-naphthyl)benzidine (hereinafter, abbreviated as NPD), a benzidine derivative such as N,N,N',N'-tetraphenylbenzidine or 1,1-bis[4-(di-4-methylamino)phenyl]cyclohexane (hereinafter, abbreviated as It is TAPC), or various triphenylamine trimers and tetramers. These compounds may be formed into a single film. However, they may be used as a single layer mixed with other materials to form a film, or may be formed into a plurality of layers formed separately, a plurality of layers formed by mixing, or a layer formed separately and mixed. The layered structure of the layers of the film. Further, as the injection and transport layer of the hole, a coating type such as poly(3,4-ethylenedioxythiophene) (hereinafter abbreviated as PEDOT)/polystyrene sulfonate (hereinafter abbreviated as PSS) may be used. Polymer material. In addition to the vapor deposition method, film formation of these materials can be carried out by a known method such as a spin coating method or an inkjet method.

Further, in the hole injection layer or the hole transport layer, a material which is further P-doped with a material commonly used in the layer, such as trisbromophenylamine hexachloroantimonate, or a partial structure thereof may be used. A polymer compound such as a TPD structure.

As the electron blocking layer of the organic EL device of the present invention, in addition to the compound having the indolocarbazole ring structure represented by the formula (1) of the present invention, 4,4',4"-tris(N-咔 can be used. Zozolyl triphenylamine (hereinafter, abbreviated as TCTA), 9,9-bis[4-(carbazol-9-yl)phenyl]anthracene, 1,3-bis(carbazol-9-yl)benzene (below) , abbreviated as mCP), 2,2-bis(4-carbazol-9-ylphenyl)adamantane (hereinafter, abbreviated as Ad-Cz) and other carbazole derivatives, and 9-[4-(carbazole) -9-yl)phenyl]-9-[4-(triphenylsulfanyl)phenyl]-9H-indole represented by a compound having a triphenyldecylalkyl group and a triarylamine structure and having an electron blocking effect These compounds may be formed into a single film, or may be used as a single layer mixed with other materials to form a film, or may be formed into a plurality of layers formed separately, a plurality of layers formed by mixing, or a layer formed and mixed separately. The laminated structure of the film-formed layer. In addition to the vapor deposition method, film formation of these materials can be performed by a well-known method such as a spin coating method or an inkjet method.

As the light-emitting layer of the organic EL device of the present invention, in addition to the metal complex of the quinolinol derivative including Alq ₃ , various metal complexes, onion derivatives, bisstyrylbenzene derivatives, and anthracene can be used. Derivatives, oxazole derivatives, polyparaphenylene vinyl derivatives, and the like. Further, the light-emitting layer may be composed of a host material and a dopant material, and as the host material, in addition to the compound having an indolocarbazole ring structure represented by the formula (1) of the present invention, in addition to the above-mentioned light-emitting material, A thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative or the like can be used. Further, as the dopant material, quinophthalone, α-piperone, erythritol, hydrazine, and derivatives of the materials, benzopyran derivatives, rose derivatives, and aminostyryl groups can be used. Derivatives, etc. These compounds may be formed into a single film. However, they may be used as a single layer mixed with other materials to form a film, or may be formed into a plurality of layers formed separately, a plurality of layers formed by mixing, or a layer formed separately and mixed. The layered structure of the layers of the film.

Further, as the luminescent material, a phosphorescent luminescent material can also be used. As the phosphorescent emitter, a phosphorescent emitter of a metal complex such as ruthenium or platinum can be used. A green phosphorescent emitter such as Ir(ppy) ₃ , a blue phosphorescent emitter such as FIrpic or FIr6, a red phosphorescent emitter such as Btp ₂ Ir(acac), or the like is used; as a host material at this time, it is used as a hole injection and The transportable host material may be a general formula of the present invention, in addition to a 4,4'-bis(N-carbazolyl)biphenyl (hereinafter abbreviated as CBP), TCTA, or a carbazole derivative such as mCP. (1) A compound having an indolocarbazole ring structure. As a host material for electron transport, p-bis(triphenylsulfonyl)benzene (hereinafter, abbreviated as UGH2) or 2,2',2"-(1,3,5-phenylene)-parallel can be used. (1-Phenyl-1H-benzimidazole) (hereinafter, abbreviated as TPBI), etc., can produce a high-performance organic electroluminescent element.

When doping the host material of the phosphorescent material, in order to avoid concentration quenching, doping is preferably performed by co-evaporation in a range of 1 to 30% by weight based on the entire light-emitting layer.

In addition to the vapor deposition method, film formation of these materials can be carried out by a known method such as a spin coating method or an inkjet method.

As the hole barrier layer of the organic EL device of the present invention, in addition to 2,9-dimethyl-4,7-diphenyl-1,10-phenanthophenone (hereinafter abbreviated as BCP), etc. a morpholine derivative or a metal complex of a quinolinol derivative such as bis(2-methyl-8-hydroxyquinoline)-4-phenylphenolate aluminum (III) (hereinafter abbreviated as BAlq), A compound having a hole blocking action such as various rare earth complexes, oxazole derivatives, triazole derivatives, and triazabenzene derivatives can be used. These materials can also serve as materials for the electron transport layer. These compounds may be formed into a single film. However, they may be used as a single layer mixed with other materials to form a film, or may be formed into a plurality of layers formed separately, a plurality of layers formed by mixing, or a layer formed separately and mixed. The layered structure of the layers of the film. In addition to the vapor deposition method, film formation of these materials can be carried out by a known method such as a spin coating method or an inkjet method.

As the electron transport layer of the organic EL device of the present invention, in addition to the metal complex of the quinolinol derivative including Alq ₃ and BAlq, various metal complexes, triazole derivatives, and triazine derivatives can be used. And oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silole derivatives, and the like. These compounds may be formed into a single film. However, they may be used as a single layer mixed with other materials to form a film, or may be formed into a plurality of layers formed separately, a plurality of layers formed by mixing, or a layer formed separately and mixed. The layered structure of the layers of the film. In addition to the vapor deposition method, film formation of these materials can be carried out by a known method such as a spin coating method or an inkjet method.

The electron injecting layer of the organic EL device of the present invention may be an alkali metal salt such as lithium fluoride or cesium fluoride, an alkaline earth metal salt such as magnesium fluoride or a metal oxide such as alumina, but in the electron transport layer and the cathode. In the preferred selection, it can be omitted.

As the cathode of the organic EL device of the present invention, an electrode material having a low work function such as aluminum or an alloy having a lower work function such as a magnesium-silver alloy, a magnesium-indium alloy or an aluminum-magnesium alloy can be used as the electrode material.

Hereinafter, the embodiments of the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

[Example 1]

<12,12-Dimethyl-10-phenyl-7-(9-phenyl-9H-indazol-3-yl)-10,12-dihydroindeno[2,1-b]carbazole Synthesis of Compound 5) >

18.5 g of N-(9,9-dimethyl-9H-thin-2-yl)-2-bromo-phenylamine, 6.98 g of potassium acetate, and 95 ml of DMF were added to a reaction vessel after nitrogen substitution, and nitrogen gas was introduced thereto. hour. 1.18 g of hydrazine (triphenylphosphine)palladium was added and heated, and the mixture was stirred at 100 ° C for 11 hours. After cooling to room temperature, the reaction solution was poured into 300 ml of water, and then extracted with 300 ml of toluene. The organic layer was washed twice with water (200 ml) and dried over anhydrous magnesium sulfate, and then evaporated The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene/n-hexane) to give 12,12-dimethyl-10,12-dihydroindole[2,1-b. The light yellow powder of carbazole was 7.9 g (yield 55.2%).

The obtained 12,12-dimethyl-10,12-dihydroindolo[2,1-b]carbazole 7.8 g, iodine benzene 3.7 ml, sodium hydrogen sulfite 0.43 g, copper powder 0.17 g, 3, 0.69 g of 5-di(tributyl)thanoic acid, 5.71 g of potassium carbonate, and 10 ml of dodecylbenzene were added to a reaction vessel after nitrogen substitution, and the mixture was heated, and stirred at 170 ° C for 10 hours. After cooling to 100 ° C, 100 ml of toluene was added for extraction, concentration was carried out under reduced pressure, and crystallization was carried out using 30 ml of n-hexane to obtain 12,12-dimethyl-10-phenyl-10,12-di. Light yellow powder of hydroquinone [2,1-b]carbazole 8.73 g (yield 88.3%).

7.5 g of the obtained 12,12-dimethyl-10-phenyl-10,12-dihydroindolo[2,1-b]carbazole and 53 ml of DMF were added to the reaction vessel. Under ice cooling, 3.72 g of N-bromosuccinimide was added and stirred for 9 hours, and then left overnight. 260 ml of water was added, and filtration was carried out to obtain a brownish white powder of 7-bromo-12,12-dimethyl-10-phenyl-10,12-dihydroindolo[2,1-b]carbazole. 8.67 g (yield 94.6%).

7-bromo-12,12-dimethyl-10-phenyl-10,12-dihydroindolo[2,1-b]carbazole 2.0 g, 9-phenyl-3-(4, Mixture of 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-indazole 1.68 g, toluene/ethanol (4/1, v/v) 15 ml of a solvent and 3.4 ml of a 2 M aqueous potassium carbonate solution were added to a reaction vessel after nitrogen substitution, and nitrogen gas was supplied thereto for 30 minutes while irradiating ultrasonic waves. 0.26 g of hydrazine (triphenylphosphine)palladium was added and heated, and the mixture was stirred at 73 ° C for 5 hours. After cooling to room temperature, 30 ml of toluene and 20 ml of water were added to conduct liquid separation, and the organic layer was collected. After the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, the crude product was obtained by concentration under reduced pressure. The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane) to give 12,12-dimethyl-10-phenyl-7-(9-phenyl-9H 1.5 mg (yield 54.7%) of a white powder of -oxazol-3-yl)-10,12-dihydroindolo[2,1-b]carbazole.

The structure of the obtained white powder was identified by NMR. The results of ¹ H-NMR measurement are shown in Fig. 1 .

The following 32 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.66(1H), 8.64(1H), 8.59(1H), 8.23-8.29(1H), 7.88-7.90(1H), 7.83-7.85(1H), 7.78-7.80(1H), 7.66- 7.71 (8H), 7.42-7.53 (7H), 7.37-7.40 (1H), 7.31-7.33 (1H), 7.26-7.29 (1H), 7.21-7.24 (1H), 1.51 (6H).

[Example 2]

Synthesis of <12,12-Dimethyl-10-phenyl-7-(4-diphenylamino-phenyl)-10,12-dihydroindolo[2,1-b]carbazole (Compound 6) >

7-Bromo-12,12-dimethyl-10-phenyl-10,12-dihydroindolo[2,1-b]carbazole synthesized in Example 1 2.0 g, 4-diphenylamino group 15 ml of phenylboric acid, 15 ml of a mixed solvent of toluene/ethanol (4/1, v/v), and 3.4 ml of a 2 M potassium carbonate aqueous solution were added to a reaction vessel after nitrogen substitution, and nitrogen gas was introduced while irradiating ultrasonic waves. minute. 0.26 g of hydrazine (triphenylphosphine)palladium was added and heated, and the mixture was stirred at 73 ° C for 5 hours. After cooling to room temperature, 30 ml of toluene and 20 ml of water were added to conduct liquid separation, and the organic layer was collected. After the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, the crude product was obtained by concentration under reduced pressure. The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene/n-hexane) to give 12,12-dimethyl-10-phenyl-7-(4-diphenylamino)- Pale yellowish white powder of phenyl)-10,12-dihydroindolo[2,1-b]carbazole 1.6 g (yield 58.4%).

The structure of the obtained white powder was identified by NMR. The results of ¹ H-NMR measurement are shown in Fig. 2 .

The following 34 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.60(1H), 8.50(1H), 7.85-7.86(1H), 7.64-7.69(7H), 7.48-7.52(2H), 7.40-7.43(2H), 7.30-7.32(1H), 7.24-7.26(4H), 7.21-7.22(1H), 7.17-7.18(2H), 7.11-7.13(4H), 6.98-7.01(2H), 1.49(6H).

[Example 3]

<12,12,12',12'-tetramethyl-10,10'-diphenyl-10,10',12,12'-tetrahydro-[7,7'] bis(indole[2, Synthesis of 1-b]oxazolyl) (Compound 102) >

7-bromo-12,12-dimethyl-10-phenyl-10,12-dihydroindolo[2,1-b]carbazole 4g, bis(pinacol) synthesized in Example 1. 2.27 g of diboron, 2.69 g of potassium acetate, and 40 ml of dimethylarylene were added to a reaction vessel after nitrogen substitution, and nitrogen gas was passed through for 30 minutes. Addition of [1,1'-bis(diphenylphosphino)ferrocene]dichloride palladium(II) (1,1'-Bis(diphenylphosphino)ferrocene-palladium(II) dichloride) The mixture (1:1) was 0.22 g and heated, and stirred at 90 ° C for 12 hours. After cooling to room temperature, 150 ml of toluene and 200 ml of saturated brine were added to conduct liquid separation, and the organic layer was collected. The organic layer was washed three times with 100 ml of saturated brine and dried over anhydrous magnesium sulfate. The crude product was purified by column chromatography (carrier: silica gel, eluent: ethyl acetate / n-hexane) to give 12,12-dimethyl-10-phenyl-7- (4,4, White powder with 5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-10,12-dihydroindeno[2,1-b]carbazole 1.89 g (yield 42.7%).

12,12-Dimethyl-10-phenyl-7-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)- 10,12-dihydroindolo[2,1-b]carbazole 1.8 g, 7-bromo-12,12-dimethyl-10-phenyl-10,12-dihydrogen synthesized in Example 1. 1.55 g of hydrazino [2,1-b]carbazole, 15 ml of a mixed solvent of toluene/ethanol (4/1, v/v), and 2.6 ml of a 2 M potassium carbonate aqueous solution were added to a reaction vessel after nitrogen substitution, while irradiating the super The sound wave was purged with nitrogen for 30 minutes. 0.20 g of hydrazine (triphenylphosphine)palladium was added and heated, and stirred at 73 ° C for 9 hours. After cooling to room temperature, the precipitated solid was collected by filtration. 80 ml of tetrahydrofuran was added to the precipitate to dissolve it, and after insoluble matter was removed by filtration, the crude product was obtained by concentration under reduced pressure. By refining the crude product using 10 ml of 1,2-dichlorobenzene, 12,12,12',12'-tetramethyl-10,10'-diphenyl-10,10' was obtained. 1.01 g (yield 39.9%) of a white powder of 12,12'-tetrahydro-[7,7'] bis(indolo[2,1-b]carbazole).

The structure of the obtained white powder was identified by NMR. The results of ¹ H-NMR measurement are shown in Fig. 3 .

The following 40 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.68(4H), 7.90-7.91(2H), 7.82-7.84(2H), 7.69-7.73(8H), 7.51-7.55(2H), 7.51(2H), 7.48-7.49(2H), 7.44-7.45 (2H), 7.32-7.35 (2H), 7.22-7.25 (2H), 1.52 (12H).

[Embodiment 4]

<7-[4-{(biphenyl-4-yl)-anilino}-phenyl]-12,12-dimethyl-10-phenyl-10,12-dihydroindole[2,1- b] Synthesis of carbazole (Compound 7) >

7-Bromo-12,12-dimethyl-10-phenyl-10,12-dihydroindolo[2,1-b]carbazole 3.0g, (biphenyl-4) synthesized in Example 1. -yl)-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]-phenylamine 3.7 g, toluene/ethanol (4 50 ml of a mixed solvent of /1, v/v) and 10 ml of a 2 M aqueous potassium carbonate solution were added to a reaction vessel after nitrogen substitution, and nitrogen gas was supplied thereto for 30 minutes while irradiating ultrasonic waves. 0.4 g of hydrazine (triphenylphosphine)palladium was added and heated, and stirred at 73 ° C for 8 hours. After cooling to room temperature, the precipitated crude product was collected by filtration. 140 ml of 1,2-dichlorobenzene was added to the crude product, and the mixture was dissolved while heating, and the insoluble matter was removed by filtration, and then the filtrate was concentrated under reduced pressure. By performing recrystallization using 100 ml of 1,2-dichlorobenzene, 7-[4-{(biphenyl-4-yl)-anilino}-phenyl]-12,12-dimethyl group was obtained. White powder of -10-phenyl-10,12-dihydroindeno[2,1-b]carbazole 2.7 g (yield 57.8%).

The structure of the obtained white powder was identified by NMR. The results of ¹ H-NMR measurement are shown in Fig. 4 .

The following 38 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.60(1H), 8.50(1H), 7.85(1H), 7.72-7.65(7H), 7.61(2H), 7.55(2H), 7.52(1H), 7.47(1H), 7.43-7.37 (4H), 7.31-7.16 (11H), 7.03 (1H), 1.49 (6H).

[Embodiment 5]

<7-[4-{bis(biphenyl-4-yl)amino}-phenyl]-12,12-dimethyl-10-phenyl-10,12-dihydroindole[2,1- b] Synthesis of carbazole (Compound 8) >

7-Bromo-12,12-dimethyl-10-phenyl-10,12-dihydroindolo[2,1-b]carbazole 3.0g, bis(biphenyl) synthesized in Example 1. 4-yl)-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]amine 4.3 g, toluene/ethanol (4 50 ml of a mixed solvent of /1, v/v) and 10 ml of a 2 M aqueous potassium carbonate solution were added to a reaction vessel after nitrogen substitution, and nitrogen gas was supplied thereto for 30 minutes while irradiating ultrasonic waves. 0.4 g of hydrazine (triphenylphosphine)palladium was added and heated, and stirred at 73 ° C for 8 hours. After cooling to room temperature, the precipitated crude product was collected by filtration. 140 ml of 1,2-dichlorobenzene was added to the crude product, and the mixture was dissolved while heating, and the insoluble matter was removed by filtration, and then the filtrate was concentrated under reduced pressure. By performing recrystallization by recrystallization of 100 ml of 1,2-dichlorobenzene, 7-[4-{bis(biphenyl-4-yl)amino}-phenyl]-12,12-dimethyl group was obtained. White powder of -10-phenyl-10,12-dihydroindeno[2,1-b]carbazole 3.7 g (yield 71.6%).

The structure of the obtained white powder was identified by NMR. The results of ¹ H-NMR measurement are shown in Fig. 5 .

The following 42 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.60(1H), 8.52(1H), 7.85(1H), 7.75-7.57(15H), 7.53(1H), 7.47(1H), 7.43-7.38(6H), 7.32-7.22(10H) , 1.49 (6H).

[Embodiment 6]

<10-(Biphenyl-4-yl)-12,12-dimethyl-7-(9-phenyl-9H-carbazol-3-yl)-10,12-dihydroindole[2,1 -b] Synthesis of carbazole (Compound 122) >

35.5 g of 12,12-dimethyl-10,12-dihydroindolo[2,1-b]carbazole synthesized in Example 1, 35.0 g of 4-bromobiphenyl, and 6.0 g of sodium hydrogen sulfite. 2.4 g of copper powder, 9.4 g of 3,5-di(tributyl) ruthenic acid, 31.2 g of potassium carbonate, and 52 ml of dodecylbenzene were added to a reaction vessel after nitrogen substitution, and heated, and stirred at 190 ° C. hour. After cooling to 120 ° C, 35 ml of toluene was added and stirred, and the crude product was collected by filtration. To the crude product, 1.6 L of toluene was added and heated, and after extracting at 110 ° C, it was cooled to room temperature, and concentrated under reduced pressure. White powder of 10-(biphenyl-4-yl)-12,12-dimethyl-10,12-dihydroindolo[2,1-b]carbazole was obtained by crystallization from 120 ml of methanol. The body was 48.5 g (yield 88.1%).

Adding 42.5 g of 10-(biphenyl-4-yl)-12,12-dimethyl-10,12-dihydroindolo[2,1-b]carbazole and DMF 2.5L to the reaction vessel After heating to 70 ° C to dissolve it, it was cooled to room temperature, and 17.4 g of N-bromo-succinimide was added and stirred for 7 hours. 2.5 L of water was added, and filtration was carried out to obtain 10-(biphenyl-4-yl)-7-bromo-12,12-dimethyl-10,12-dihydroindole[2,1-b]. The white powder of carbazole was 34.9 g (yield 69.5%).

The obtained 10-(biphenyl-4-yl)-7-bromo-12,12-dimethyl-10,12-dihydroindolo[2,1-b]carbazole 16.5 g, 9-phenyl -3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-indazole 14.2 g, toluene/ethanol (4/1, v 250 ml of a mixed solvent of /v) and 48 ml of a 2 M aqueous potassium carbonate solution were added to a reaction vessel after nitrogen substitution, and nitrogen gas was supplied thereto for 30 minutes while irradiating ultrasonic waves. 1.9 g of cerium (triphenylphosphine)palladium was added and heated, and stirred at 73 ° C for 5 hours. After cooling to room temperature, the precipitated crude product was collected by filtration. 450 ml of 1,2-dichlorobenzene was added to the crude product, and the mixture was dissolved while heating, and the insoluble matter was removed by filtration, and then the filtrate was concentrated under reduced pressure. By performing refining using 150 ml of 1,2-dichlorobenzene and 300 ml of n-hexane to obtain 10-(biphenyl-4-yl)-12,12-dimethyl-7-(9-phenyl group) White powder of -9H-carbazol-3-yl)-10,12-dihydroindeno[2,1-b]carbazole 9.8 g (yield 45.2%).

The structure of the obtained white powder was identified by NMR. The results of ¹ H-NMR measurement are shown in Fig. 6 .

The following 36 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.69(1H), 8.64(1H), 8.59(1H), 8.28(1H), 7.99(2H), 7.89(1H), 7.85-7.78(6H), 7.66(4H), 7.56-7.49 (6H), 7.44-7.37 (4H), 7.32 (1H), 7.27 (1H), 7.23 (1H), 1.52 (6H).

[Embodiment 7]

<10-(Biphenyl-4-yl)-7-[4-bis(biphenyl-4-yl)amino-phenyl]-12,12-dimethyl-10,12-dihydroindrene[ Synthesis of 2,1-b]carbazole (Compound 123) >

10-(Biphenyl-4-yl)-7-bromo-12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole synthesized in Example 6 13.0 g , bis(biphenyl-4-yl)-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]amine 15.9 g 250 ml of a mixed solvent of toluene/ethanol (4/1, v/v) and 51 ml of a 2 M potassium carbonate aqueous solution were added to a reaction vessel after nitrogen substitution, and nitrogen gas was supplied thereto for 30 minutes while irradiating ultrasonic waves. 2.1 g of hydrazine (triphenylphosphine)palladium was added and heated, and stirred at 73 ° C for 10 hours. After cooling to room temperature, the precipitated crude product was collected by filtration. 1.7 L of 1,2-dichlorobenzene was added to the crude product, which was dissolved while heating, and the insoluble matter was removed by filtration, and then cooled to room temperature. The precipitated solid was collected by filtration, and purified by recrystallization using 1.7 L of 1,2-dichlorobenzene to obtain 10-(biphenyl-4-yl)-7-[4-bis(biphenyl). White powder of -4-yl)amino-phenyl]-12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole 13.4 g (yield 63.8%).

The structure of the obtained white powder was identified by NMR. The results of ¹ H-NMR measurement are shown in Fig. 7 .

The following 46 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ (ppm) = 8.62 (1H), 8.54 (1H), 7.98 (2H), 7.86 (1H), 7.78 (4H), 7.75 (2H), 7.70 (1H), 7.63 (4H), 7.58 (4H), 7.55 (1H), 7.50 (3H), 7.43 (1H), 7.40 (4H), 7.33-7.21 (11H), 1.51 (6H).

[Embodiment 8]

<12,12-Dimethyl-10-(9,9-dimethyl-9H-indol-2-yl)-7-(9-phenyl-9H-indazol-3-yl)-10,12 -Synthesis of dihydroindolo[2,1-b]carbazole (Compound 124) >

12,12-Dimethyl-10,12-dihydroindolo[2,1-b]oxazole 5.5g, 2-bromo-9,9-dimethyl-9H- synthesized in Example 1.茀 6.4g, sodium hydrogen sulfite 0.3g, copper powder 0.1g, 3,5-di (tri-butyl) sulphate 0.5g, potassium carbonate 4.0g, and dodecylbenzene 5ml added to the reaction after nitrogen substitution The vessel was heated and stirred at 180 ° C for 29 hours. After cooling to 100 ° C and adding 80 ml of toluene, the insoluble matter was removed by filtration and concentrated. By using crystallization of 20 ml of n-hexane, 12,12-dimethyl-10-(9,9-dimethyl-9H-indol-2-yl)-10,12-dihydroindole[2] was obtained. , 1-b] oxazole loess toner 7.4 g (yield 80.0%).

12,12-Dimethyl-10-(9,9-dimethyl-9H-indol-2-yl)-10,12-dihydroindolo[2,1-b]carbazole 7.0 g 140 ml of DMF was added to the reaction vessel, and after heating to 100 ° C to dissolve it, it was cooled. Under ice cooling, 2.6 g of N-bromo-succinimide was added, and the mixture was stirred at room temperature for 1 hour. 500 ml of water was added, and filtration was carried out to obtain 7-bromo-12,12-dimethyl-10-(9,9-dimethyl-9H-indol-2-yl)-10,12-dihydroanthracene. And the reddish powder of [2,1-b]carbazole was 5.7 g (yield 70.3%).

7-Bromo-12,12-dimethyl-10-(9,9-dimethyl-9H-indol-2-yl)-10,12-dihydroindeno[2,1-b] 4.0 g of carbazole, 3.2 g of 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole, 50 ml of a mixed solvent of toluene/ethanol (4/1, v/v) and 10 ml of a 2 M aqueous potassium carbonate solution were added to a reaction vessel after nitrogen substitution, and nitrogen gas was supplied thereto for 30 minutes while irradiating ultrasonic waves. 0.4 g of hydrazine (triphenylphosphine)palladium was added and heated, and stirred at 71 ° C for 7 hours. After cooling to room temperature, 20 ml of water was added to carry out liquid separation, and the organic layer was collected. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene/cyclohexane) to give 12,12-dimethyl-10-(9,9-dimethyl-9H-茀-2-yl)-7-(9-phenyl-9H-carbazol-3-yl)-10,12-dihydroindeno[2,1-b]carbazole white powder 3.4g The rate is 65.7%).

The structure of the obtained white powder was identified by NMR. The results of ¹ H-NMR measurement are shown in Fig. 8 .

The following 40 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ(ppm)=8.67(1H), 8.65(1H), 8.60(1H), 8.28(1H), 8.08(1H), 7.90-7.82(5H), 7.69-7.66(5H), 7.58-7.49(5H) 7.43 (2H), 7.39 (2H), 7.36 (1H), 7.33 (1H), 7.28 (1H), 7.23 (1H), 1.61 (6H), 1.51 (6H).

[Embodiment 9]

For the compound of the present invention, the glass transition point was determined by a high-sensitivity differential scanning calorimeter (manufactured by Bruker-AXS, DSC3100S).

The compound of the present invention has a glass transition point of 100 ° C or more, indicating that the film state of the compound of the present invention is stable.

[Embodiment 10]

Using the compound of the present invention, a vapor deposited film having a thickness of 100 nm was produced on the ITO substrate, and the work function was measured by an atmospheric photoelectron spectroscope (manufactured by Riken Keiki Co., Ltd., AC-3 type).

As shown above, it can be understood that the compound of the present invention is compared with the work function 5.4eV of a general hole transporting material such as NPD or TPD, which exhibits a suitable energy level and has good hole transporting ability.

[Embodiment 11]

As shown in FIG. 9, on the glass substrate 1 on which the ITO electrode as the transparent anode 2 is formed in advance, the hole injection layer 3, the hole transport layer 4, the light-emitting layer 5, the electron transport layer 6, and the electrons are sequentially vapor-deposited. An organic EL element was produced by injecting the layer 7 and the cathode (aluminum electrode) 8.

Specifically, after the glass substrate 1 on which ITO having a film thickness of 150 nm was formed was washed with an organic solvent, the surface was washed by an oxygen plasma treatment. Thereafter, the glass substrate having the ITO electrode was mounted in a vacuum vapor deposition machine, and the pressure was reduced to 0.001 Pa or less. Next, the compound 125 of the following structural formula was formed to have a film thickness of 20 nm so as to cover the transparent anode 2 as the hole injection layer 3. On the hole injection layer 3, the compound (Compound 5) of Inventive Example 1 was formed to have a film thickness of 40 nm as the hole transport layer 4. On the hole transport layer 4, the compound 126 of the following formula and the compound 127 of the following formula were subjected to binary vapor deposition at a vapor deposition rate of the compound 126: compound 127 = 5:95. A film thickness of 30 nm was formed as the light-emitting layer 5. On the light-emitting layer 5, Alq _{3 was} formed to have a film thickness of 30 nm as the electron transport layer 6. On the electron transport layer 6, lithium fluoride was formed to have a film thickness of 0.5 nm as the electron injection layer 7. Finally, aluminum was vapor-deposited to a film thickness of 150 nm to form a cathode 8. The characteristics of the organic EL device produced were measured in the air at room temperature.

The measurement results of the luminescence characteristics when a DC voltage was applied to the organic EL device produced by using the compound (Compound 5) of Example 1 of the present invention are shown in Table 1.

[化131]

[化132]

[化133]

[Embodiment 12]

The material of the hole transport layer 4 in Example 11 was replaced by the compound (Compound 6) of Example 2 of the present invention, and an organic EL element was produced under the same conditions as in Example 11. The characteristics of the organic EL device produced were measured in the air at room temperature. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were collectively shown in Table 1.

[Example 13]

The material of the hole transport layer 4 in Example 11 was replaced by the compound (Compound 7) of the present invention, and an organic EL device was produced under the same conditions as in Example 11. The characteristics of the organic EL device produced were measured in the air at room temperature. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were collectively shown in Table 1.

[Embodiment 14]

The material of the hole transport layer 4 in Example 11 was replaced by the compound (Compound 8) of the present invention, and an organic EL device was produced under the same conditions as in Example 11. The characteristics of the organic EL device produced were measured in the air at room temperature. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were collectively shown in Table 1.

[Example 15]

The material of the hole transport layer 4 in Example 11 was replaced by the compound (Compound 122) of the present invention, and an organic EL device was produced under the same conditions as in Example 11. The characteristics of the organic EL device produced were measured in the air at room temperature. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were collectively shown in Table 1.

[Example 16]

An organic EL device was produced under the same conditions as in Example 11 except that the material of the hole transport layer 4 in Example 11 was replaced by the compound (Compound 123) of the present invention. The characteristics of the organic EL device produced were measured in the air at room temperature. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were collectively shown in Table 1.

[Example 17]

The material of the hole transport layer 4 in Example 11 was replaced by the compound (Compound 124) of the present invention, and an organic EL device was produced under the same conditions as in Example 11. The characteristics of the organic EL device produced were measured in the air at room temperature. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were collectively shown in Table 1.

[Comparative Example 1]

For comparison, an organic EL device was produced under the same conditions as in Example 11 except that the material of the hole transport layer 4 in Example 11 was replaced with the above compound B. The characteristics of the organic EL device produced were measured in the air at room temperature. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were collectively shown in Table 1.

[Comparative Example 2]

For comparison, the material of the hole transport layer 4 in Example 11 was replaced with the compound 128 of the following structural formula, and an organic EL element was produced under the same conditions as in Example 11. The characteristics of the organic EL device produced were measured in the air at room temperature. The measurement results of the luminescence characteristics when a DC voltage was applied to the produced organic EL device were collectively shown in Table 1.

[化134]

As shown in Table 1, the driving voltage at a current having a current density of 10 mA/cm ² was 5.62 V of the compound B, and the compounds of Examples 1 to 2 and 4 to 8 of the present invention (Compounds 5 to 8, 122~124) is 4.77~5.46V, and all of them are low voltage.

Further, in terms of power efficiency, the compounds (compounds 5 to 8, 122 to 124) of Examples 1 to 2 and 4 to 8 of the present invention were 5.30 to 6.34 lm/W with respect to 5.06 lm/W of the compound B, both of which were A substantial increase.

Further, the compounds (Compounds 122 to 124) of Examples 6 to 8 of the present invention were 5.64 to 6.76 lm/W, which were also improved with respect to 5.49 lm/W of the compound 128; in particular, the present invention 1~ 2. The compound of 4~5 (compound 5~8) is 5.84~6.34lm/W, which is greatly improved.

From the above results, it is apparent that the organic EL device using the compound having the indolocarbazole ring structure of the present invention can achieve an improvement in power efficiency and a practical driving voltage as compared with the organic EL device using the above-mentioned compound B of the present invention. The reduction. Further, it can be understood that the power source efficiency can be improved even when compared with the organic EL element using the compound 128 which is known as a high-performance hole transport material.

[Industry use possibility]

The compound having an indolocarbazole ring structure of the present invention is excellent as a compound for an organic EL device because of its high hole transporting ability, excellent electron blocking ability, excellent amorphousness, and stable film state. By using the compound to produce an organic EL device, not only high luminous efficiency and power supply efficiency can be obtained, but also a practical driving voltage can be lowered, and durability can be improved. For example, it can be extended to household electrical appliances or lighting applications.

1. . . glass substrate

2. . . Transparent anode

3. . . Hole injection layer

4. . . Hole transport layer

5. . . Luminous layer

6. . . Electronic transport layer

7. . . Electron injection layer

8. . . cathode

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a ¹ H-NMR chart of the compound (Compound 5) of Example 1 of the present invention.

Fig. 2 is a ¹ H-NMR chart of the compound (Compound 6) of Example 2 of the present invention.

Figure 3 is a ¹ H-NMR chart of the compound (Compound 102) of Example 3 of the present invention.

Figure 4 is a ¹ H-NMR chart of the compound (Compound 7) of Example 4 of the present invention.

Figure 5 is a ¹ H-NMR chart of the compound (Compound 8) of Example 5 of the present invention.

Figure 6 is a ¹ H-NMR chart of the compound (Compound 122) of Example 6 of the present invention.

Figure 7 is a ¹ H-NMR chart of the compound (Compound 123) of Example 7 of the present invention.

Figure 8 is a ¹ H-NMR chart of the compound (Compound 124) of Example 8 of the present invention.

Fig. 9 is a view showing the structures of organic EL elements of Examples 11 to 17 and Comparative Examples 1 and 2.

1. . . glass substrate

2. . . Transparent anode

3. . . Hole injection layer

4. . . Hole transport layer

5. . . Luminous layer

6. . . Electronic transport layer

7. . . Electron injection layer

8. . . cathode

Claims (11)

A compound having an indolocarbazole ring structure represented by the following formula (1): (wherein A represents a substituted or unsubstituted aromatic hydrocarbon or a substituted or unsubstituted condensed polycyclic aromatic divalent group; and Ar ₁ , Ar ₂ and Ar ₃ may be the same or different from each other, and Ar ₂ represents no. a substituted phenyl group, Ar ₁ , Ar ₃ represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; here, A and Ar _{2 is formed by} a single bond, an oxygen atom, or a sulfur atom to form a ring, and Ar ₂ and Ar _{3 are} not bonded to each other to form a ring; R ₁ to R ₉ may be the same or different from each other, and are a hydrogen atom and a heavy hydrogen atom. a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, may have a substituent a cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group a cyclic, substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom. R ₁₀ and R ₁₁ may be the same or different from each other, and may be a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and 5 to 10 carbon atoms which may have a substituent. a cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 10 carbon atoms having a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substitution Or an unsubstituted aryloxy group may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring). A compound having an indolocarbazole ring structure as claimed in claim 1 is represented by the following formula (3): (In the formula, A represents a substituted or unsubstituted aromatic hydrocarbon or a substituted or unsubstituted condensed polycyclic aromatic divalent group, and Ar ₁ , Ar ₂ and Ar ₃ may be the same or different, and Ar ₂ means no. a substituted phenyl group, Ar ₁ , Ar ₃ represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; here, A and Ar _{2 is formed by} a single bond, an oxygen atom, or a sulfur atom to form a ring, and Ar ₂ and Ar _{3 are} not bonded to each other to form a ring; R ₁ to R ₉ may be the same or different from each other, and are a hydrogen atom and a heavy hydrogen atom. a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, may have a substituent a cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group a cyclic, substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom. R ₁₀ and R ₁₁ may be the same or different from each other, and may be a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and 5 to 10 carbon atoms which may have a substituent. a cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 10 carbon atoms having a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group or a substituted or The unsubstituted aryloxy group may also be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring). A compound having an indolocarbazole ring structure according to claim 1 or 2, wherein in the above formula (1) or (3), R ₁₀ and R ₁₁ may have a substituent having 1 to 1 carbon atom. a linear or branched alkyl group of 6 or a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, A linear or branched alkoxy group having 1 to 6 carbon atoms which may have a substituent, or a cycloalkoxy group having 5 to 10 carbon atoms which may have a substituent. A compound having an indolocarbazole ring structure as in the second aspect of the patent application, wherein in the above formula (3), A is a substituted or unsubstituted phenyl group. A compound having an indolocarbazole ring structure as claimed in claim 2, which is represented by the following formula (3-3): (wherein, Ar ₁ and Ar ₃ may be the same or different from each other, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group. R ₁ to R ₉ may be the same or different from each other, and are a hydrogen atom, a heavy hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear group having 1 to 6 carbon atoms which may have a substituent or a branched alkyl group, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a carbon which may have a substituent a linear or branched alkoxy group having 1 to 6 atoms, a cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group a heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which may also be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom. Form a ring). A compound having an indolocarbazole ring structure as claimed in claim 5, which is represented by the following formula (3-4): (wherein Ar ₁ represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; and R ₁ to R ₉ may be the same as each other. Differently, it is a hydrogen atom, a heavy hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and may have a substituent. a cycloalkyl group having 5 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched carbon number of 1 to 6 which may have a substituent Alkoxy group, cycloalkyloxy group having 5 to 10 carbon atoms which may have a substituent, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensation The cycloaromatic group or the substituted or unsubstituted aryloxy group may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring). An organic electroluminescence device comprising an organic electroluminescent device having a pair of electrodes and an organic layer sandwiching at least one layer therebetween, characterized in that: an indolocarbazole having the first aspect of the patent application is used. The compound of the ring structure serves as a constituent material of at least one organic layer. The organic electroluminescent device of claim 7, wherein the organic layer is a hole transport layer. The organic electroluminescent device of claim 7, wherein the organic layer is an electron blocking layer. The organic electroluminescent device of claim 7, wherein the organic layer is a hole injection layer. An organic electroluminescence device according to claim 7, wherein the organic layer is a light-emitting layer.